利用光驱动的生物杂合系统实现CO_(2)转化生产化学品

太阳能作为清洁能源之一,为缓解化石燃料枯竭和温室气体排放等问题提供了一种高效、经济、可持续的解决方案.自然界中的植物和光合微生物通过自身的光合系统收集并转化太阳能,从而生产生物燃料和生物化学品.然而,由于自然光合系统存在光吸收范围相对较窄、光生电子在传输过程中易损耗等问题,限制了太阳能到化学品的转化效率.为了解决上述难题,科研人员模仿自然光合作用中的关键部分,探索构建人工光合系统,相关研究引起了广泛关注.本文通过将碲化镉量子点(CdTe QDs)与大肠杆菌(E.coli)相耦合,构建了一种光驱动无机-生物杂合系统(IBPHS),用于捕获太阳能并驱动CO_(2)转化合成高价值化学品.该系统主要由光催化模块和生物催化模块组成.在光催化模块中,通过生物合成CdTe QDs进行光能捕获,并将其转化为电子.通过敲除E.coli的Cd2+外排蛋白(ZNTA)编码基因,实现了E.coli胞内Cd2+过量积累.通过“时空耦合”方式,并借助共聚焦显微镜、高分辨率透射电镜和X射线能谱分析,确认了CdTe QDs在E.coli胞内的组装合成.利用紫外-可见分光光度计研究了光催化模块对光子的吸收能力.结果表明,光催化模块的吸收峰位于400-420 nm.利用瞬时光电流,评估了光催化模块的光生电子能力.实验发现,该模块可以产生0.07μA光电流,表明完成了光催化模块的构建.在生物催化模块中,将光催化模块产生的电子用于还原NAD+再生NADH.采用NADH生物传感器,分析了E.coli胞内NADH含量,结果表明,在蓝光照射下E.coli胞内NADH含量比黑暗条件下提高了5.1倍.在此基础上,通过表达NADH依赖型乳酸脱氢酶(LDH)将丙酮酸还原为乳酸,在蓝光光照下乳酸积累量达到了0.44 g/L,而黑暗条件下无乳酸积累,从而验证了生物催化模块的有效性.基于光催化模块和生物催化模块,进一步组装构建了IBPSH,用于驱动CO_(2)还原合成甲酸和丙酮酸.在蓝光照射下,IBPHS能够合成0.65 g/L甲酸和0.18 g/L丙酮酸,其CO_(2)利用速率分别达到51.98 mg/gDCW/h和21.92 mg/gDCW/h,超过了光合细菌.综上所述,本文利用光催化模块与生物催化模块相耦合的方式,组装构建了一种新型的人工光合系统,实现了光驱动CO_(2)还原合成高附加值化学品,为理性设计材料-生物杂合系统提供了借鉴,同时也为挖掘绿色生物制造潜力、开发太阳能化学制造平台提供参考.

Nonlinear Seebeck and Peltier effects in a Majorana nanowire coupled to leads

We theoretically study nonlinear thermoelectric transport through a topological superconductor nanowire hosting Majorana bound states(MBSs) at its two ends, a system named as Majorana nanowire(MNW). We consider that the MNW is coupled to the left and right normal metallic leads subjected to either bias voltage or temperature gradient. We focus our attention on the sign change of nonlinear Seebeck and Peltier coefficients induced by mechanisms related to the MBSs, by which the possible existence of MBSs might be proved. Our results show that for a fixed temperature difference between the two leads, the sign of the nonlinear Seebeck coefficient(thermopower) can be reversed by changing the overlap amplitude between the MBSs or the system equilibrium temperature, which are similar to the cases in linear response regime. By optimizing the MBS–MBS interaction amplitude and system equilibrium temperature, we find that the temperature difference may also induce sign change of the nonlinear thermopower. For zero temperature difference and finite bias voltage, both the sign and magnitude of nonlinear Peltier coefficient can be adjusted by changing the bias voltage or overlap amplitude between the MBSs. In the presence of both bias voltage and temperature difference, we show that the electrical current at zero Fermi level and the states induced by overlap between the MBSs keep unchanged, regardless of the amplitude of temperature difference. We also find that the direction of the heat current driven by bias voltage may be changed by weak temperature difference.

Microstructure and mechanical performance of AZ31/6061 lap joints welded by laser-TIG hybrid welding with Zn-Al alloy filler metal

A series of Zn-xAl(x=0-35 wt.%)alloy filler metals were designed to join AZ31 Mg alloy to 6061 Al alloy by laser-TIG hybrid welding.The effect of Al content on the wettability of filler metals,microstructure evolution and strength of joint was investigated.The results indicated that the strength of joints was improved with the increase of Al content in filler metals.When Zn-15Al filler was used,the ultimate fracture load reached the maximum of 1475.3 N/cm,which was increased by 28%than that with pure Zn filler.The reason is that the Al element acts as a"reaction depressant"in filler metal,which contributes to inhibiting the dissolution of Mg base metal and the Mg-Zn reaction.The addition of appropriate quantity of Al element promoted the precipitation of Al-rich solid solution instead of Zn solid solution.The MgZn_(2) IMCs have lower lattice mismatch with Al solid solution than Zn solid solution,thus the strength of joints is improved.However,the excessive addition of Al caused the formation of brittle Mg32(Al,Zn)49 ternary compounds,leading to the deterioration of joint performance.

An Opposition-Based Learning-Based Search Mechanism for Flying Foxes Optimization Algorithm

The flying foxes optimization(FFO)algorithm,as a newly introduced metaheuristic algorithm,is inspired by the survival tactics of flying foxes in heat wave environments.FFO preferentially selects the best-performing individuals.This tendency will cause the newly generated solution to remain closely tied to the candidate optimal in the search area.To address this issue,the paper introduces an opposition-based learning-based search mechanism for FFO algorithm(IFFO).Firstly,this paper introduces niching techniques to improve the survival list method,which not only focuses on the adaptability of individuals but also considers the population’s crowding degree to enhance the global search capability.Secondly,an initialization strategy of opposition-based learning is used to perturb the initial population and elevate its quality.Finally,to verify the superiority of the improved search mechanism,IFFO,FFO and the cutting-edge metaheuristic algorithms are compared and analyzed using a set of test functions.The results prove that compared with other algorithms,IFFO is characterized by its rapid convergence,precise results and robust stability.

Distributed Virtual Inertia Based Control of Multiple Photovoltaic Systems in Autonomous Microgrid

The large inertia of a traditional power system slows down system's frequency response but also allows decent time for controlling the system.Since an autonomous renewable microgrid usually has much smaller inertia,the control system must be very fast and accurate to fight against the small inertia and uncertainties.To reduce the demanding requirements on control,this paper proposes to increase the inertia of photovoltaic(PV) system through inertia emulation.The inertia emulation is realized by controlling the charging/discharging of the direct current(DC)-link capacitor over a certain range and adjusting the PV generation when it is feasible and/or necessary.By well designing the inertia,the DC-link capacitor parameters and the control range,the negative impact of inertia emulation on energy efficiency can be reduced.The proposed algorithm can be integrated with distributed generation setting algorithms to improve dynamic performance and lower implementation requirements.Simulation studies demonstrate the effectiveness of the proposed solution.

Efficient synthesis of tyrosol from L-tyrosine via heterologous Ehrlich pathway in Escherichia coli

For the efficient conversion of L-tyrosine(L-Tyr)to tyrosol,which is an aromatic compound widely used in the pharmaceutical and chemical industries,a novel four-enzyme cascade pathway based on the Ehrlich pathway of Saccharomyces cerevisiae was designed and reconstructed in Escherichia coli.Then,the expression levels of the relevant enzymes were coordinated using a modular approach and gene duplication after the identification of the pyruvate decarboxylase from Candida tropicalis(CtPDC)as the rate-limiting enzymatic step.In situ product removal(ISPR)strategy with XAD4 resins was explored to avoid product inhibition and further improve tyrosol yield.As a result,the titer and conversion rate of tyrosol obtained were 35.7 g·L^(-1) and 93.6%,respectively,in a 3-L bioreactor.Results presented here provide a potential enzymatic process for industrial production of tyrosol from cheap amino acids.

Ultrasonic Welding of Magnesium–Titanium Dissimilar Metals:A Study on Thermo-mechanical Analyses of Welding Process by Experimentation and Finite Element Method

Ultrasonic welding is an effective ways to achieve a non-reactive/immiscible heterogeneous metal connection, such as the connection of magnesium alloy and titanium alloy. But the thermal mechanism of magnesium alloy/titanium alloy ultrasonic welding has not been defined clearly. In this paper, the experimental and the finite element analysis were adopted to study the thermal mechanism during welding. Through the test, the temperature variation law during the welding process is obtained, and the accuracy of the finite element model is verified. The microscopic analysis indicates that at the welding time of 0.5 s, the magnesium alloy in the center of the solder joint is partially melted and generates the liquid phase. Through the finite element analysis, the friction coefficient of the magnesium–titanium ultrasonic welding interface can be considered as an average constant value of 0.28. The maximum temperature at the interface can exceed 600 ℃ to reach the melting point temperature of the magnesium alloy. The plastic deformation begins after 0.35 s and occurs at the magnesium side at the center of the interface.

Enhancement of α-ketoisovalerate production by relieving the product inhibition of L-amino acid deaminase from Proteus mirabilis

L-Amino acid deaminase(LAAD) is a key enzyme in the deamination of L-valine(L-val) to produce α-ketoisovalerate(KIV). However, the product inhibition of LAAD is a major hindrance to industrial KIV production.In the present study, a combination strategy of modification of flexible loop regions around the product binding site and the avoidance of dramatic change of main-chain dynamics was reported to reduce the product inhibition.The four mutant PM-LAAD^(M4)(PM-LAAD^(S98A/T105A/S106A/L341A)) achieved a 6.2-fold higher catalytic efficiency and an almost 6.7-fold reduction in product inhibition than the wild-type enzyme. Docking experiments suggested that weakened interactions between the product and enzyme, and the flexibility of the "lid" structure relieved LAAD product inhibition. Finally, the whole-cell biocatalyst PM-LAAD^(M4) has been applied to KIV production,the titer and conversion rate of KIV from L-val were 98.5 g·L^-1 and 99.2% at a 3-L scale, respectively. These results demonstrate that the newly engineered catalyst can significantly reduce the product inhibition, that making KIV a prospective product by bioconversion method, and also provide the understanding of the mechanism of the relieved product inhibition of PM-LAAD.

Preparation and performance analysis of a coking coal dust suppressant spray

Coking coal dust is extremely hydrophobic;therefore,combination with droplets in the air is difficult and dust suppression is challenging.Here,a dust suppressant spray for coking coal dust was studied in order to improve of the combination of droplets and coking coal dust.Based on monomer optimization and compounding analysis,two surfactant monomers,fatty alcohol ether sodium sulfate(AES)and sodium dodecyl benzene sulfonate(SDBS)were selected as the surfactant components of the dust suppressant.The surfactant monomers were combined with four inorganic salts and the reverse osmosis moisture absorption of each solution was determined.By combining the reverse osmosis moisture absorption values with the water retention experimental results,CaCl_(2)was identified as the optimal inorganic salt additive for the dust suppressant.Finally,the optimal concentration of each component was obtained using orthogonal experimental design i.e.,AES(0.03%),SDBS(0.05%),and CaCl_(2)(0.4%).The dust suppressant solution formulated using this method had a high moisture absorption capacity and excellent performance.

Exsolved materials for CO_(2)reduction in high-temperature electrolysis cells

Electrochemical reduction of CO_(2)into valuable fuels and chemicals has become a contemporary research area,where the heterogeneous catalyst plays a critical role.Metal nanoparticles supported on oxides performing as active sites of electrochemical reactions have been the focus of intensive investigation.Here,we review the CO_(2)reduction with active materials prepared by exsolution.The fundamental of exsolution was summarized in terms of mechanism and models,materials,and driven forces.The advances in the exsolved materials used in hightemperature CO_(2)electrolysis were catalogued into tailored interfaces,synergistic effects on alloy particles,phase transition,reversibility and electrochemical switching.

Enhanced spin-dependent thermopower in a double-quantum-dot sandwiched between two-dimensional electron gases

We study the spin-dependent thermopower in a double-quantum-dot(DQD) embedded between the left and right two-dimensional electron gases(2DEGs) in doped quantum wells under an in-plane magnetic field. When the separation between the DQD is smaller than the Fermi wavelength in the 2DEGs, the asymmetry in the dots' energy levels leads to pronounced quantum interference effects characterized by the Dicke line-shape of the conductance, which are sensitive to the properties of the 2DEGs. The magnitude of the thermopower, which denotes the generated voltage in response to an infinitesimal temperature difference between the two 2DEGs under vanishing charge current, will be obviously enhanced by the Dicke effect. The application of the in-plane magnetic field results in the polarization of the spin-up and spin-down conductances and thermopowers, and enables an efficient spin-filter device in addition to a tunable pure spin thermopower in the absence of its charge counterpart.

Concentration-Dependent Effect of Nickel Ions on Amyloid Fibril Formation Kinetics of Hen Egg White Lysozyme:a Raman Spectroscopy Study

Nickel,an important transi-tion metal element,is one of the trace elements for hu-man body and has a crucial impact on life and health.Some evidences show the excess exposure to metal ions might be associated with neurological diseases.Herein,we applied Raman spectroscopy to study the Ni(II)ion effect on kinetics of amyloid fibrillation of hen egg white lysozyme(HEWL)in thermal and acidic conditions.Using the well-known Raman indicators for protein tertiary and secondary structures,we monitored and analyzed the concentration effect of Ni(II)ions on the unfolding of tertiary structures and the transformation of sec-ondary structures.The experimental evidence validates the accelerator role of the metal ion in the kinetics.Notably,the additional analysis of the amide I band profile,combined with thioflavin-T fluorescence assays,clearly indicates the inhibitory effect of Ni(II)ions on the formation of amyloid fibrils with organizedβ-sheets structures.Instead,a more significant promotion influence is affirmed on the assembly into other aggregates with disordered struc-tures.The present results provide rich information about the specific metal-mediated protein fibrillation.

Hole‑Transport Management Enables 23%‑Efficient and Stable Inverted Perovskite Solar Cells with 84%Fill Factor

NiO_(x)-based inverted perovskite solar cells(PSCs)havepresented great potential toward low-cost,highly efficient and stablenext-generation photovoltaics.However,the presence of energy-levelmismatch and contact-interface defects between hole-selective contacts(HSCs)and perovskite-active layer(PAL)still limits device efficiencyimprovement.Here,we report a graded configuration based on bothinterface-cascaded structures and p-type molecule-doped compositeswith two-/three-dimensional formamidinium-based triple-halideperovskites.We find that the interface defects-induced non-radiativerecombination presented at HSCs/PAL interfaces is remarkably suppressedbecause of efficient hole extraction and transport.Moreover,astrong chemical interaction,halogen bonding and coordination bondingare found in the molecule-doped perovskite composites,whichsignificantly suppress the formation of halide vacancy and parasitic metallic lead.As a result,NiO_(x)-based inverted PSCs present a power-conversion-efficiency over 23%with a high fill factor of 0.84 and open-circuit voltage of 1.162 V,which are comparable to the best reported around 1.56-electron volt bandgap perovskites.Furthermore,devices with encapsulation present high operational stability over 1,200 h during T_(90) lifetime measurement(the time as a function of PCE decreases to 90%of its initial value)under 1-sun illumination in ambient-air conditions.

Two-dimensional hexagonal Zn3Si2 monolayer:Dirac cone material and Dirac half-metallic manipulation

The fascinating Dirac cone in honeycomb graphene,which underlies many unique electronic properties,has inspired the vast endeavors on pursuing new two-dimensional(2D)Dirac materials.Based on the density functional theory method,a 2D material Zn3Si2 of honeycomb transition-metal silicide with intrinsic Dirac cones has been predicted.The Zn3Si2 monolayer is dynamically and thermodynamically stable under ambient conditions.Importantly,the Zn3Si2 monolayer is a room-temperature 2D Dirac material with a spin-orbit coupling energy gap of 1.2 meV,which has an intrinsic Dirac cone arising from the special hexagonal lattice structure.Hole doping leads to the spin polarization of the electron,which results in a Dirac half-metal feature with single-spin Dirac fermion.This novel stable 2D transition-metal-silicon-framework material holds promises for electronic device applications in spintronics.

Risk Factors for Prognosis after the Maze Ⅳ Procedure in Patients with Atrial Fibrillation Undergoing valve Surgery

The present study evaluated risk factors related to persistent atrial fibrillation(AF)at discharge(AF-d)and recurrent atrial fibrillation(rAF)and all-cause death after the maze IV procedure.Two hundred nineteen patients(63 female,aged 52.5±8.8 years)with valve disease and persistent AF undergoing valve surgery and the maze IV procedure in our center between 2015 and 2016 were included.Baseline demographic and clinical data were obtained by review of medical records.The median follow-up period was 27 months(interquartile range 21-34 months)in our patient cohort.The primary end point was all-cause death.The secondary end point was AF-d or rAF.rAF is defined as AF recurrence at 3 months or later after the procedure.Twenty-eight patients(12.8%)died during follow-up.Multiple logistic regression analysis showed that thrombocytopenia,elevated serum total bilirubin level,a larger right atrium,AF-d,and rAF were independent determinants for all-cause death after the maze IV procedure after adjustment for age,sex,and clinical covariates,including New York Heart Association class III/IV disease,hypertension,and aortic regurgitation,while valvular disease duration and left atrial diameter greater than 80.5 mm were independent determinants for AF-d,and thrombocytopenia,elevated serum total bilirubin level,higher mean pulmonary artery pressure,and AF-d were independent predictors for rAF.In conclusion,thrombocytopenia,elevated serum total bilirubin level,an enlarged right atrium,AF-d,and rAF are independent predictors of all-cause death in patients undergoing the maze IV procedure.

Photoacoustic molecular imaging with functional nanoparticles

Photoacoustic imaging(PAI)breaks through the optical di®usion limit by making use of the PA e®ect.By converting incident photons into ultrasonic waves,PAI combines high contrast of optical imaging and high spatial resolution in depth tissue of ultrasound imaging in a single imaging modality.This imaging modality has now shown potential for molecular imaging,which enables visualization of biological processes with systemically introduced functional nanoparticles.In the current review,the potentials of di®erent optical nanoprobes as PAI contrast agents were elucidated and discussed.

High-sensitivity intelligent packaging films harnessing rose anthocyanins and hydrophilic silica aerogel for visual food freshness monitoring

The enhancement of the sensitivity for anthocyanin-based indicator films in food freshness monitoring in real time is important for application.In this study,hydrophilic silica aerogel(SiO2 NA)was incorporated into corn starch(CS)/chitosan(CH)/rose anthocyanins(RACNs)-encapsulated potato amylopectin nanoparticles(APNPs)composite film to increase the sensitivity for shrimp freshness detection.The microstructure of films revealed that the gas absorption capacity was improved by amorphous SiO2 NA via hydrogen interactions.The pore size(1.74–5.60 times),pore volume(3.92–5.60 times),and specific surface area(2.21–2.34 times)of films increased with the addition of SiO2 NA.The sensing of NH3 and pH and the reversibility of films were also reinforced.Meanwhile,the pH-responsive films containing SiO2 NA changed visibly in color from purple–red to orange–gray and finally to gray,enabling effective monitoring of shrimp freshness during storage at 4°C.Thus,anthocyanin-based indicator films with improved sensitivity by adding SiO2 NA were successfully designed for monitoring shrimp freshness.

支持向量机的关键问题和展望

作为机器学习的主要方法之一,支持向量机不仅有坚实的统计学习理论基础,而且在众多领域中表现出优秀的泛化性能,因此受到了广泛关注.然而近几年来,相比于深度学习的蓬勃发展,支持向量机的研究进展缓慢.本文从支持向量机的本质出发,探讨支持向量机的理论方法与深度学习等机器学习热点研究的交叉与融合,提出一些新的思路.具体地,包括3个方面:支持向量机的大间隔原则及其带来的低密度性、核映射的高维划分技巧及其统计学习理论,以及支持向量机的浅层学习模式向深度学习和广度学习的拓展.同时,从这3个方面分别提出支持向量机研究中可以进一步挖掘的优良性质,并展望未来可能诱导出的理论和方法.

重组大肠杆菌全细胞催化L-苏氨酸合成2,5-二甲基吡嗪

2,5-二甲基吡嗪(2,5-dimethylpyrazine,2,5-DMP)在食品香料与医药方面具有重要的经济价值,工业上普遍采用环境不友好且反应条件苛刻的化学合成法来生产。文中结合代谢工程和辅因子工程策略设计高效催化L-苏氨酸合成2,5-DMP的全细胞催化剂,实现微生物转化法合成2,5-DMP。本研究首先分析了不同微生物来源的苏氨酸脱氢酶(Threonine dehydrogenase,TDH)对2,5-DMP合成的影响,发现来源于大肠杆菌Escherichia coli中EcTDH具有最佳的催化能力,2,5-DMP产量达到(438.3±23.7)mg/L。随后结合辅因子工程,通过引入乳脂链球菌Lactococcus cremoris中NADH氧化酶(NADH oxidase,LcNox E)并优化其表达方式发现通过融合表达EcTDH和Lc Nox E可平衡胞内NADH/NAD+水平,维持较高细胞存活率,进一步提高2,5-DMP产量。最后,通过阻断合成2,5-DMP的支路代谢途径,可以显著减少副产物积累,增加2,5-DMP产量,同时提高L-苏氨酸转化率。最终获得的重组菌EcΔkΔAΔBΔA/TDHEcNoxELc-PSst T在含有5 g/L L-苏氨酸的转化体系中于37℃、200 r/min孵化24 h,可积累(1095.7±81.3)mg/L的2,5-DMP,L-苏氨酸转化率达到76%,产物得率为0.288 g/(g L-苏氨酸)。因此,文中构建的重组菌可以实现高效催化L-苏氨酸合成2,5-DMP,具有一定的工业应用潜力。

一种可促进重组蛋白表达量和稳定性的多功能纯化标签的开发与利用

自组装双亲短肽(Self-assembling amphipathic peptides,SAPs)是一类亲疏水氨基酸按一定规律分布、具有自聚合效应的短肽,融合在酶蛋白N端时,具有促进表达和稳定化的功能。根据前期研究结论,设计一条全新的基于SAPs (S1vw,HNANARARHNANARARHNANARARHNARARAR)的可促进融合蛋白表达和稳定性,并可用于镍柱亲和层析的多功能短肽标签,在大肠杆菌表达系统中,将S1vw以PT-linker(PTPPTTPTPPTTPTP)融合在碱性果胶酶(Alkaline polygalacturonate lyase,PGL)、脂肪氧合酶(Lipoxygenase,LOX)及绿色荧光蛋白(Green fluorescent protein,GFP)的N末端时,与对应的野生型相比,PGL及LOX的粗酶活分别提高了3.1倍和1.89倍,GFP的荧光强度提高了16.22倍。S1vw的3种融合酶均可用镍柱进行亲和纯化,并具有较高的回收率。PGL及LOX在对应的热处理条件下,与野生型相比,半衰期分别提高了2.16倍和3.2倍。将GFP-S1vw在枯草芽孢杆菌及毕赤酵母表达系统中表达,发现在枯草芽孢杆菌中融合蛋白表达量提高明显,但在毕赤酵母中表达量几乎没有改变。说明在原核表达体系中,S1vw可作为一种新型的促表达、稳定化及可纯化的多功能标签。